Radiation-sensitive resin composition

ABSTRACT

A radiation-sensitive resin composition comprising an alkali-soluble novolak resin and a 1,2-quinonediazide compound, wherein the alakli-soluble novolak resin comprises a mixture of: 
     95-50 parts by weight of Resin A having a standard polystyrene-reduced weight-average molecular weight of 2,000-20,000 [Resin A is at least one resin selected from the group consisting of a resin obtained by polycondensation of m-cresol and at least one phenol represented by the structural formula (I) or (I&#39;): ##STR1## wherein m is 2 or 3, with at least one aldehyde and a resin obtained by polycondensation of m-cresol, p-cresol and at least one phenol repreented by the above structural formula (I) or (I&#39;) with at least one aldehyde] and 
     5-50 parts by weight of Resin B having a standard polystyrene-reduced weight-average molecular weight of 200-2,000 [Resin B is a resin obtained by polycondensation of at least one phenol represented by the structural formula (II): ##STR2## wherein n is 0, 1, 2 or 3, with at least one aldehyde]. In the resin composition, the mixture of Resin A and Resin B may further contain Resin C which is an ester of Resin B with a 1,2-quinonediazidesulfonic acid. The radiation-sensitive resin compopsition is suitable for use as a positive type resist having high sensitivity, excellent developability, high resolution and excellent heat resistance.

This application is a Continuation of application Ser. No. 08/032,392filed on Mar. 15, 1993, now abandoned, which is a CON of 07/841,300,filed Feb. 28, 1992, now abandoned; which is a CON of 07/464,673, filedJan. 10, 1990, now abandoned; which is a CIP of 07/421,328, filed Oct.13, 1989, now abandoned.

This invention relates to a radiation-sensitive resin composition. Moreparticularly, this invention relates to a radiation-sensitive resincomposition suitable for use as a positive type resist which issensitive to radiations such as ultraviolet rays, deep ultraviolet rays,X-rays, electron beam, molecular beam, gamma rays, synchrotronradiation, proton beam and the like and which is used for production ofhighly integrated circuits.

Positive type resists are being used in a large amount in the productionof integrated circuits because a resist pattern of high resolution canbe obtained from the positive type resists.

The recent progress of integrated circuits into a higher integrationrequires a positive type resist capable of forming a resist pattern ofhigher resolution. That is, when a positive type resist is used to forma fine resist pattern, the resist is exposed to a light to form a latentimage and then developed with a developing solution (an aqueous alkalisolution) to obtain an image; at this time, it is necessary that theexposed portion can be developed rapidly to its part contacting thewafer, i.e. the foot of the pattern. In conventional positive typeresists, when they are used to form a resist pattern having aline-to-line distance of 1 μm or less, the developability at the foot ofthe resist pattern is poor and the degree of resolution becomes low.

With an enhancement of the integration degree of integrated circuits,wafer etching system is changing from the conventional wet etching (thisgives large side etching) to dry etching (this gives small sideetching). In this dry etching, it is necessary that the resist patterndoes not change during the etching and accordingly a heat-resistantresist is required to be used. Conventional positive type resists cannotbe considered to have sufficient heat resistance.

An object of this invention is to solve the above-mentioned problems ofthe prior art and to provide a radiation-sensitive resin compositionwhich is suitable for use as a positive type resist having a highsensitivity, an excellent developability, a high resolution andexcellent heat resistance.

Other objects and advantages of this invention will become apparent fromthe following description.

According to this invention, there is provided a radiation-sensitiveresin composition comprising an alkali-soluble novolac resin and a1,2-quinonediazide compound, wherein the alkali-soluble novolac resincomprises a mixture of:

95-50 parts by weight of Resin A having a standard polystyrene-reducedweight-average molecular weight of 2,000-20,000 [Resin A is at least oneresin selected from the group consisting of a resin obtained bypolycondensation of m-cresol and at least one phenol represented by thestructural formula (I) or (I'): ##STR3## wherein m is 2 or 3, with atleast one aldehyde and a resin obtained by polycondensation of m-cresol,p-cresol and at least one phenol represented by the above structuralformula (I) or (I') with at least one aldehyde] and

5-50 parts by weight of Resin B having a standard polystyrene-reducedweight-average molecular weight of 200-2,000 [Resin B ms a resinobtained by polycondensation of at least one phenol represented by thestructural formula (II): ##STR4## wherein n is 0, 1, 2 or 3, with atleast one aldehyde] (the resin composition is hereinafter referred to as"Composition A").

According to this invention, there is further provided aradiation-sensitive resin composition comprising an alkali-solublenovolak resin and a 1,2-quinonediazide compound, wherein thealkali-soluble novolak resin comprises a mixture of:

50-95 parts by weight of Resin A having a standard polystyrene-reducedweight-average molecular weight of 2,000-20,000 [Resin A is at least oneresin selected from the group consisting of a resin obtained bypolycondensation of m-cresol and at least one phenol represented by thestructural formula (I) or (I'): ##STR5## wherein m is 2 or 3, with atleast one aldehyde and a resin obtained by polycondensation of m-cresol,p-cresol and at least one phenol represented by the above structuralformula (I) or (I') with at least one aldehyde],

0-45 parts by weight of Resin B having a standard polystyrene-reducedweight-average molecular weight of 200-2,000 [Resin B is a resinobtained by polycondensation of at least one phenol represented by thestructural formula (II): ##STR6## wherein n is 0, 1, 2 or 3, with atleast one aldehyde], and

5-50 parts by weight of Resin C (Resin C is an ester of Resin B with1,2-quinonediazidesulfonic acid) (the resin composition is hereinafterreferred to as "Composition B").

The phenols represented by the structural formulas (I) and (I')[hereinafter referred to as "the phenols (I)"] used in this inventioninclude 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol,2,3,5-trimethylphenol and 3,4,5-trimethylphenol. Of these, 3,5-xylenoland 2,3,5-trimethylphenol are preferred.

The phenols represented by the structural formula (II) [hereinafterreferred to as "the phenols (II)"] include phenol, o-cresol, m-cresol,p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol,3,4-xylenol, 3,5-xylenol, 3,6-xylenol, 2,3,5-trimethylphenol and3,4,5-trimethylphenol. Of these, m-cresol, o-cresol, p-cresol,3,5-xylenol and 2,3,5-trimethylphenol are preferred.

The phenols (I) can be used alone or in admixture of two or more, andthe phenols (II) can also be used alone or in admixture of two or more.

The aldehyde used in this invention includes formaldehyde,paraformaldehyde, benzaldehyde, furfural and acetaldehyde. Of these,formaldehyde is particularly preferred. These aldehydes can be usedalone or in asmixture of two or more.

Resin A used in this invention has a standard polytyrene-reducedweight-average molecular weight (hereinafter referred to as "Mw") of2,000-20,000, preferably 4,000-20,000 and particularly is obtained bypolycondensation of m-cresol and at least one of the phenols (I) orm-cresol, p-cresol and at least one of the phenols (I) with at least oneof the aldehydes in the presence of an acidic catalyst. When the Mw ismore than 20,000, it is difficult to uniformly coat the resultingcomposition on a wafer and the resulting composition has reduceddevelopability and reduced sensitivity. When the Mw is less than 2,000,the resulting composition has reduced heat resistance.

Also, Resin A is preferably such that when the maximum heights of peaksof a curve obtained by gel permeation chromatography in the ranges ofpolystyrene-reduced weight-average molecular weight of from 6,300 to25,000, from 2,500 to 6,000 and from 150 to 900 are defined as a, b andc, respectively, a/b=0-1.5 and c/b=0-2, and more preferably such thata/b=0.2-1.3 and c/b=0-1.5. In some cases, when the a/b value exceeds1.5, the developability and sensitivity are deteriorated and when thec/b value exceeds 2, the heat resistance and developability aredeteriorated.

Resin B used in this invention has a Mw of 200-2,000, preferably300-1,000 and is obtained by polycondensation of at least one of thephenols (II), preferably m-cresol and at least one of the phenols (II)other than m-cresol with at least one of the aldehydes in the presenceof an acidic catalyst. When the Mw is more than 2,000, the resultingcomposition has reduced sensitivity and reduced developability. When theMw is less than 200, the composition has reduced heat resistance.

The amounts of m-cresol, p-cresol, at least one of the phenols (I) andat least one of the phenols (II) used (these phenols are hereinafterreferred to generically as "the phenols") are such that in Resin A, themolar ratio of m-cresol/the phenols (I) is usually 20/80 to 95/5,preferably 40/60 to 95/5, more preferably 50/50 to 90/10 in the casewhere m-cresol and the phenols (I) are used in combination and the molarratio of m-cresol/p-cresol/the phenols (I) is usually 20-90/5-75/5-75,preferably 40-80/10-50/10-50 in the case where m-cresol, p-cresol andthe phenols (I) are used in combination, and in Resin B, the molar ratioof m-cresol/the phenols (II) other than m-cresol is preferably 95/5 to5/95.

An acidic catalyst is used in the above polycondensations, and it may bean inorganic acid such as hydrochloric acid, nitric acid, sulfuric acidor the like, or an organic acid such as formic acid, oxalic acid, aceticacid or the like.

The amount of the aldehyde used is preferably 0.7-3 moles, particularlypreferably 0.8-1.5 moles, per mole of the phenols in the case of ResinA, and preferably 0.1-1.5 moles, particularly preferably 0.15-0.6 mole,per mole of the phenols in the case of Resin B. The amount of the acidiccatalyst used is usually 1×10⁻⁵ to 5×10⁻¹ mole per mole of the phenols.

Water is ordinarily used as a reaction medium in the polycondensation. Ahydrophilic solvent may be used as a reaction medium when the phenolsused in the polycondensation are insoluble in an aqueous solution of thealdehyde and the reaction system becomes non-uniform from the start ofthe reaction. The hydrophilic solvent includes, for example, alcoholssuch as methanol, ethanol, propanol, butanol and the like, and cyclicethers such as tetrahydrofuran, dioxane and the like. The amount of thereaction medium is usually 20-1,000 parts by weight per 100 parts byweight of the reaction materials.

The polycondensation temperature can be varied appropriately dependingupon the reactivities of the reactants but is usually 10°-200° C.,preferably 70°-130° C.

The polycondensation can be effected according to, for example, a methodwherein the phenols, the aldehyde, the acidic catalyst, etc. are chargedat one time, or a method wherein the phenols, the aldehyde, etc. areadded gradually with the progress of the reaction, in the presence of anacidic catalyst.

After the completion of the polycondensation, in order to remove theunreacted materials, acidic catalyst and reaction medium present in thesystem, the internal temperature of the reaction vessel is generallyelevated to 130°-230° C. and made vacuum (e.g. about 20-50 mmHg) todistil off the volatile components, thereby recovering Resin A or B.

In order to obtain Resin A having a high Mw, it is possible to dissolvethe recovered resin in a good solvent such as ethyl cellosolve acetate,dioxane, methanol or the like, mix the resulting solution with a poorsolvent such as water, n-hexane, n-heptane or the like and separate theprecipitated resin solution layer to recover Resin A on the highermolecular weight side.

In Composition A of this invention, the amount of Resin A is 95-50 partsby weight, preferably 90-60 parts by weight, and the amount of Resin Bis 5-50 parts by weight, preferably 10-40 parts by weight (the totalamount of Resins A and B is 100 parts by weight). When the amount ofResin A is more than 95 parts by weight, the resulting composition haspoor developability. When the amount is less than 50 parts by weight,the resulting composition has reduced heat resistance.

Resin C used in Composition B of this invention can be obtained byesterifying Resin B with a 1,2-quinonediazidesulfonic acid chloride inthe presence of a basic catalyst. Preferably, Resin B used in thiscondensation has a Mw of 200-1,500.

The 1,2-quinonediazidesulfonic acid chloride includes1,2-benzoquinonediazide-4-sulfonic acid chloride,1,2-naphthoquinonediazide-4-sulfonic acid chloride,1,2-naphthoquinonediazide-5-sulfonic acid chloride, etc. Of these,preferred are 1,2-naphthoquinonediazide-5-sulfonic acid chloride(hereinafter referred to as "NQD-5") and1,2-naphthoquinonediazide-4-sulfonic acid chloride (hereinafter referredto as "NQD-4").

The basic catalyst includes amines such as trimethylamine,triethylamine, diethylamine, tripropylamine, tributylamine, pyridine andthe like, and inorganic alkalis such as sodium hydroxide, potassiumhydroxide and the like. The amount of the basic catalyst used is usually0.8-2 moles, preferably 1-1.5 moles, per mole of the1,2-quinonediazidesulfonic acid chloride. The proportion of the1,2-quinonediazidesulfonic acid chloride used to Resin B is 0.5-2.5,preferably 0.75-2 by weight.

The esterification is effected usually in the presence of a solvent. Thesolvent includes, for example, acetone, dioxane, methyl ethyl ketone,N,N-dimethylacetamide, etc. The amount of the solvent used is usually1-10 times the weight of the reactants.

An example of the purification method employed after the esterificationreaction is a method comprising removing the precipitated hydrochlorideproduced as a by-product by filtration, or dissolving the precipitatedhydrochloride in water, mixing the resulting solution with a largeamount of an aqueous acid solution (e.g. diluted hydrochloric acid) toreprecipitate the product, and then drying the product.

Resin C thus obtained has usually a Mw value of 220 to 2,500.

Also, the degree of esterification of Resin C is represented by thefollowing equation: ##EQU1## and is preferably 20-90%, particularlypreferably 25-80%. In some cases, when the degree of esterification ofResin C is less than 20%, the developability and exposure margin ofResin C are deteriorated and when it exceeds 90%, the sensitivity anddevelopability are deteriorated.

In Composition B of this invention, the amount of Resin A is 50-95 partsby weight, preferably 60-90 parts by weight, the amount of Resin B is0-45 parts by weight, preferably 5-35 parts by weight, and the amount ofResin C is 5-50 parts by weight, preferably 5-35 parts by weight, thetotal amount of Resins A, B and C being 100 parts by weight. When theamount of Resin A is more than 95 parts by weight, the resultingcomposition has reduced resolution and reduced sensitivity and theexposure margin becomes narrow. When the amount is less than 50 parts byweight, the resulting composition has reduced heat resistance. When theamount of Resin B is more than 45 parts by weight, the resultingcomposition has reduced heat resistance. When the amount of Resin C ismore than 50 parts by weight, the resulting composition has reducedsensitivity. When the amount is less than 5 parts by weight, theresulting composition has reduced developability.

The 1,2-quinonediazide compound used in Compositions A and B of thisinvention includes, for example, 1,2-benzoquinonediazide-4-sulfonic acidesters, 1,2-naphthoquinonediazide-4-sulfonic acid esters,1,2-naphthoquinonediazide-5-sulfonic acid esters, etc. Specific examplesof the 1,2-quinonediazide compound are1,2-benzoquinonediazide-4-sulfonic acid esters,1,2-naphthoquinonediazide-4-sulfonic acid esters and1,2-naphthoquinonediazide-5-sulfonic acid esters of(poly)hydroxybenzenes such as p-cresol, resorcinol, phloroglucinol,pyrogallol and the like; 1,2-benzoquinonediazide-4-sulfonic acid esters,1,2-naphthoquinonediazide-4-sulfonic acid esters and1,2-naphthoquinonediazide-5-sulfonic acid esters of (poly)hydroxyphenylalkyl ketones or (poly)hydroxyphenyl aryl ketones such as2,4-dihydroxyphenyl propyl ketone, 2,4-dihydroxyphenyl n-hexyl ketone,2,4-dihydroxybenzophenone, 2,3,4-trihydroxyphenyl n-hexyl ketone,2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone,2,3,4,4'-tetrahydroxybenzophenone,2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone,2,2',4,4'-tetrahydroxybenzophenone,2,2',3,4,6'-pentahydroxybenzophenone,2,3,3',4,4',5'-hexahydroxybenzophenone,2,3',4,4',5',6-hexahydroxybenzophenone and the like;1,2-benzoquinonediazide-4-sulfonic acid esters,1,2-naphthoquinonediazide-4-sulfonic acid esters and1,2-naphthoquinonediazide-5-sulfonic acid esters of bis [(poly)hydroxyphenyl]alkanes such as bis (p-hydroxyphenyl) methane, bis(2,4-dihydroxyphenyl) methane, bis-(2,3,4-trihydroxyphenyl) methane,2,2-bis (p-hydroxyphenyl) propane, 2,2-bis(2,4-dihydroxyphenyl)propane,2,2-bis(2,3,4-trihydroxyphenyl)propane and the like;1,2-benzoquinonediazide-4-sulfonic acid esters,1,2-naphthoquinonediazide-4-sulfonic acid esters and1,2-naphthoquinonediazide-5-sulfonic acid esters of alkyl (poly)hydroxybenzoates or aryl (poly)hydroxybenzoates such as lauryl3,5-dihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate, lauryl3,4,5-trihydroxybenzoate, propyl 3,4,5-trihydroxybenzoate, phenyl3,4,5-trihydroxybenzoate and the like;1,2-benzoquinonediazide-4-sulfonic acid esters,1,2-naphthoquinonediazide-4-sulfonic acid esters and1,2-naphthoquinonediazide-5-sulfonic acid esters of bis[poly)hydroxybenzoyl]alkanes or bis-[(poly)hydroxybenzoyl] benzenes suchas bis(2,5-dihydroxybenzoyl)methane,bis(2,3,4-trihydroxybenzoyl)methane,bis(2,4,6-trihydroxybenzoyl)methane, p-bis(2,5-dihydroxybenzoyl)benzene,p-bis(2,3,4-trihydroxybenzoyl)benzene,p-bis(2,4,6-trihdyroxybenzoyl)benzene and the like; and1,2-benzoquinonediazide-4-sulfonic acid esters,1,2-naphthoquinonediazide-4-sulfonic acid esters and1,2-naphthoquinonediazide-5-sulonic acid esters of (poly)ethylene glycoldi[(poly)hydroxybenzoates] such as ethylene glycoldi(3,5-dihydroxybenzoate), polyethylene glycoldi(3,5-dihydroxybenzoate), polyethylene glycoldi(3,4,5-trihydroxybenzoate) and the like. Besides the above compounds,there can also be used 1,2-quinonediazide compounds described in J,Kosar, "Light-Sensitive Systems", 339-352 (1965), John Wiley & Sons Co.(New York) and W. S. De Forest, "Photoresist" 50, (1975), McGraw-Hill,Inc. (New York).

Of the above 1,2-quinonediazide compounds, particularly preferable are1,2-naphthoquinonediazidesulfonic acid esters of trihydroxybenzophenonesuch as2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acidester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonicacid ester,2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acidester and2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acidester; and 1,2-naphthoquinonediazidesulfonic acid esters oftetrahydroxybenzophenone such as2,2',4,4'-tetrahydroxy-benzophenone-1,2-naphthoquinonediazide-4-sulfonicacid ester,2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonicacid ester,2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonicacid ester,2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthaoquinonediazide-5-sulfonicacid ester,2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonicacid ester and2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonicacid ester. The number (condensation ratio) of1,2-naphthoquinonediazidesulfonic acid groups bonding totrihydroxybenzophenone or tetrahydroxybenzophenone to form esterlinkages is preferably 1.5-3 on an average in the case oftrihydroxybenzophenone-1,2-naphthoquinonediazidesulfonic acid ester and2-4 on an average in the case oftetrahydroxybenzophenone-1,2-naphthoquinonediazidesulfonic acid ester.

The above 1-2-quinonediazide compounds are used alone or in admixture oftwo or more.

The amount of the 1,2-quinonediazide compound used in Composition A or Bof this invention is preferably 5-100 parts by weight, particularlypreferably 10-50 parts by weight, based on 100 parts by weight of thetotal of Resins A and B or Resins A, B and C. When the amount is toosmall, the resulting composition has no sufficient difference insolubility in developing solution, between the radiation-irradiatedportions and the non-irradiated portions, thus resulting in andifficulty in patterning. When the amount is too large, the resultingcomposition tends to have reduced developability.

Compositions A and B of this invention may further comprise a sensitizerin order to increase its sensitivity to radiations. The sensitizerincludes, for example, 2H-pyrido [3,2-b]-1,4-oxazine-3[4H]ones,10H-pyrido [3,2-b] [1,4]-benzothiazines, urazoles, hydantoins,barbituric acids, glycine anhydride, 1-hydroxybenzotriazoles, alloxans,maleimides and the like. The amount of the sensitizer used is usuallynot more than 100 parts by weight, preferably not more than 60 parts byweight, per 100 parts by weight of the 1,2-quinonediazide compound.

Moreover, the present Compositions A and B may contain a surface activeagent for improving the coatability, for example, striation, and thedevelopability of the radiation-irradiated portions after the formationof dry film. The surface active agent includes, for example, nonionicsurfactants [e.g. polyoxyethylene alkyl ethers such as polyoxyethylenelauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl etherand the like; polyoxyethylene alkylphenyl ethers such as polyoxyethyleneoctylphenyl ether, polyoxyethylene nonylphenyl ether and the like;difatty acid esters of polyethylene glycol such as polyethylene glycoldilaurate, polyethylene glycol distearate and the like];fluorine-containing surfactants such as F Top EF 301, EF 303 and EF 352(these are products of Shin Akita Kasei K.K.), Megafac F 171, F 172 andF 173 (these are products of DAINIPPON INK & CHEMICALS), Fluorad FC 430and FC 431 (these are products of Sumitomo 3M Limited), and Asahi GuardAG 710 and Surflon S-382, SC 101, SC 102, SC 103, SC 104, SC 105 and SC106 (these are products of Asahi Glass Co., Ltd.); organosiloxanepolymer KP 341 (a product of Shin-Etsu Chemical Co., Ltd.); and acrylicor methacrylic acid (co)polymers Polyflow No. 75 and No. 95 (these areproducts of Kyoeisha Yushikagaku Kogyo K.K.). The amount of the surfaceactive agent used is usually 2% by weight or less, preferably 1% byweight or less, based on the solids content of Composition A or B.

Compositions A and B of this invention may further contain a dye and apigment in order to visualize the latent image of theradiation-irradiated portions and minimize the effect of halation duringthe irradiation with a radiation, and an adhering aid in order toimprove the adhesiveness to a substrate.

Compositions A and B of this invention may further contain, ifnecessary, a storage stability improver, an antifoaming agent, etc.

The method of coating Composition A or B of this invention on asubstrate such as a silicon wafer or the like comprises dissolvingComposition A or B in a solvent so that the concentration (in terms ofsolids content) becomes, for example, 20-40% by weight, filtering theresulting solution through a filter having a pore diameter of, forexample, about 0.2 μm and coating the filtrate on a substrate such as asilicon wafer or the like by spin-coating, flow-coating, roll-coating orthe like. The solvent used in this operation includes, for example,glycol ethers such as ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether and the like; ethylene glycol alkyl ether acetates suchas methyl cellosolve acetate, ethyl cellosolve acetate and the like;diethylene glycol monoalkyl ethers such as diethylene glycol monomethylether, diethylene glycol monoethyl ether and the like; propylene glycolalkyl ether acetates such as propylene glycol methyl ether acetate,propylene glycol ethyl ether acetate, propylene glycol propyl etheracetate and the like; aromatic hydrocarbons such as toluene, xylene andthe like; ketones such as methyl ethyl ketone, cyclohexanone and thelike; and esters such as methyl 2-hydroxypropionate, ethyl2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethylethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate,3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate,3-methyl-3-methoxybutyl butyrate, ethyl acetate, butyl acetate and thelike. There can also be added high boiling solvents such as benzyl ethylether, dihexyl ether, diethylene glycol monomethyl ether, diethyleneglycol monoethyl ether, acetonylacetone, isophorone, caproic acid,caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate,ethyl benzoate, diethyl oxalate, diethyl maleate, gamma-butyrolactone,ethylene carbonate, propylene carbonate, phenyl cellosolve acetate andthe like.

As the developing solution for Composition A or B of this invention,there can be used aqueous alkali solutions obtained by dissolving inwater, for example, an inorganc alkali such as sodium hydroxide,potassium hydroxide, sodium carbonate, sodium silicate, sodiummetasilicate, ammonium water or the like; a primary amine such asethylamine, n-propylamine or the like; a secondary amine such asdiethylamine, di-n-propylamine or the like; a tertiary amine such astriethylamine, methyldiethylamine or the like; an alcoholamine such asdimethylethanolamine, triethanolamine or the like; a quaternary ammoniumsalt such as tetramethylammonium hydroxide, tetraethylammonium hydroxideor the like; or a cyclic amine such as pyrrole, piperidine,1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane orthe like.

The developing solution may further contain appropriate amounts of awater-soluble organic solvent, for example, an alcohol such as methanol,ethanol or the like, and a surface active agent as mentioned above.

This invention will be explained in more detail below referring toSynthesis Examples and Examples. However, this invention should not beinterpreted to be restricted to the Synthesis Examples and Examples.

In the Examples, Mw was measured according to a gel permeationchromatography (GPC) using GPC columns consisting of two G2000H₆columns, one G3000H₆ column and one G4000H₆ column (manufactured byTosoh Corp.) and using, as a standard, a monodisperse polystyrene underthe analytical conditions that the flow rate was 1.5 ml/min, the eluentwas tetrahydrofuran and the column temperature was 40° C.

Resist properties were evaluated according to the following testmethods.

Sensitivity

A resist was exposed to a light using a stepper (NSR1505G4D manufacturedby NIPPON KOGAKU K.K.), was subjected to development for 60 seconds at25° C. using an aqueous solution containing 2.4% by weight oftetramethylammonium hydroxide, rinsed with water, and dried to form aresist pattern on a wafer. This procedure was repeated with varying theexposure time, to examine an exposure time capable of forming a "lineand space" pattern of 0.8 μm at a 1:1 width ratio (this exposure time ishereinafter referred to as "optimum exposure time").

Resolution

The dimension of a minimum resist pattern at optimum exposure time wasmeasured.

Yield of residual film thickness

Measured were the film thickness of a resist before development and thethickness of a pattern formed from the resist. Then, a ratio of thelatter thickness to the former thickness was calculated.

Developability

The degree of scum and insufficient development seen on the resist afterdevelopment was examined.

Heat resistance

A wafer having formed thereon a resist pattern was placed in a cleanoven, and the temperature at which the pattern began to deform wasmeasured.

Exposure margin

The exposure time (E_(th)) at which the film thickness in the exposedportion becomes 0 after exposure is divided by the above optimumexposure time (E_(op)) and the exposure margin is indicated as theresulting value (E_(th) /E_(op)). The smaller this value, the broaderthe exposure margin.

Synthesis Example 1

Into a separable flask provided with a stirrer, a condenser and athermometer were charged the following materials:

    ______________________________________                                        m-Cresol            104.0  g (0.962 mol)                                      2,3,5-Trimethylphenol                                                                             14.0   g (0.103 mol)                                      37 wt. % aqueous formal-                                                                          125.3  g (1.544 mol)                                      dehyde solution                                                               (hereinafter referred                                                         to as formalin)                                                               Oxalic acid dihydrate                                                                             1.558  g (0.012 mol)                                      ______________________________________                                    

The separable flask was immersed in an oil bath, and the flask contentswere subjected to polycondensation for 1 hour with stirring whilemaintaining the flask interior at 100° C. Then, the following materialswere added:

    ______________________________________                                        m-Cresol            26.0   g (0.240 mol)                                      2,3,5-Trimethylphenol                                                                             56.1   g (0.412 mol)                                      ______________________________________                                    

Polycondensation was effected for a further 2 hours to synthesize ResinA. After the completion of the reaction, the temperature of the oil bathwas increased to 180° C. and simultaneously the pressure inside thereaction vessel was reduced to 30-40 mmHg to remove water, oxalic acid,unreacted formaldehyde and unreacted phenols. Then, the resulting moltenResin A was cooled to room temperature and recovered. Resin A wasdissolved in ethyl cellosolve acetate so that the solids concentrationbecame 20% by weight. To the resulting resin solution were addedmethanol in an amount two times the weight of the resin solution andwater in the same amount as the weight of the resin solution. Themixture was stirred and then allowed to stand. The mixture was separatedinto two layers. The resin solution layer (lower layer) was taken out,concentrated, dehydrated and dried to recover Resin A [hereinafterreferred to as "Resin A (1)"].

Resin A (1) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 8,100.

Synthesis Example 2

In the same separable flask as used in Synthesis Example 1 were chargedthe following materials:

    ______________________________________                                        m-Cresol           27.0   g (0.250 mol)                                       3,5-Xylenol        52.2   g (0.427 mol)                                       Formalin           130.3  g (1.605 mol)                                       Oxalic acid dihydrate                                                                            0.731  g (0.00580 mol)                                     ______________________________________                                    

The separable flask was immersed in an oil bath, and the flask contentswere subjected to polycondensation for 35 minutes with stirring whilemaintaining the flask interior at 100° C. Then, the following materialswere added:

    ______________________________________                                        m-Cresol          108.0  g (0.999 mol)                                        3,5-Xylenol       13.1   g (0.107 mol)                                        ______________________________________                                    

Polycondensation was effected for a further 90 minutes to synthesizeResin A. After the completion of the reaction, the temperature of theoil bath was increased to 180° C. and simultaneously the pressure insidethe reaction vessel was reduced to 30-40 mmHg to remove water, oxalicacid, unreacted formaldehyde and unreacted phenols. The same subsequentprocedure as in Synthesis Example 1 was repeated, whereby Resin A[hereinafter referred to as "Resin A (2)"] was recovered.

Resin A (2) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 7,500.

Synthesis Example 3

Into the same separable flask as used in Synthesis Example 1 werecharged the following materials:

    ______________________________________                                        m-Cresol           100.0  g (0.925 mol)                                       p-Cresol           100.0  g (0.925 mol)                                       Formalin           37.5   g (0.462 mol)                                       Oxalic acid dihydrate                                                                            0.559  g (0.0044 mol)                                      ______________________________________                                    

The separable flask was immersed in an oil bath, and the flask contentswere subjected to polycondensation for 30 minutes with stirring whilemaintaining the flask interior at 100° C. After the completion of thereaction, the temperature of the oil bath was increased to 180° C., andsimultaneously the pressure inside the reaction vessel was reduced to30-40 mmHg to remove water, oxalic acid, unreacted formaldehyde andunreacted phenols. The resulting molten resin was cooled to roomtemperature to recover Resin B [hereinafter referred to as "Resin B(1)"].

Resin B (1) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 590.

Synthesis Example 4

The same procedure as in Synthesis example 3 was repeated, except thatthe following materials were used, to synthesize Resin B [hereinafterreferred to as "Resin B (2)"]:

    ______________________________________                                        m-Cresol           175.5  g (1.623 mol)                                       2,3,5-Trimethylphenol                                                                            24.5   g (0.180 mol)                                       Formalin           36.6   g (0.451 mol)                                       Oxalic acid dihydrate                                                                            1.636  g (0.0130 mol)                                      ______________________________________                                    

Resin B (2) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 610.

Synthesis Example 5

The same procedure as in Synthesis Example 3 was repeated, except thatthe following materials were used, to synthesize Resin B C hereinafterreferred to as "Resin B (3)"]:

    ______________________________________                                        m-Cresol          114.0  g (1.056 mol)                                        3,5-Xylenol       86.0   g (0.705 mol)                                        Formalin          35.7   g (0.440 mol)                                        Oxalic acid       0.731  g (0.0058 mol)                                       ______________________________________                                    

Resin B (3) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 670.

Synthesis Example 6

Into the same separable flask as used in Synthesis Example 1 werecharged the following materials:

    ______________________________________                                        m-Cresol           19.3   g (0.178 mol)                                       p-Cresol           38.5   g (0.356 mol)                                       3,5-Xylenol        52.2   g (0.428 mol)                                       Formalin           137.3  g (1.693 mol)                                       Oxalic acid dihdyrate                                                                            0.731  g (0.00580 mol)                                     ______________________________________                                    

The separable flask was immersed in an oil bath, and flask contents weresubjected to polycondensation for 1 hour with stirring while maintainingthe flask interior at 100° C. Then, the following materials were added:

    ______________________________________                                        m-Cresol          77.0   g (0.713 mol)                                        3,5-Xylenol       13.0   g (0.107 mol)                                        ______________________________________                                    

Polycondensation was effected for a further 2 hours to synthesize ResinA. After the completion of the reaction, the temperature of the oil bathwas increased to 180° C., and simultaneously the pressure inside thereaction vessel was reduced to 30-40 mmHg to remove water, oxalic acid,unreacted formaldehyde and unreacted phenols. The same subsequentprocedure as in Synthesis Example 1 was repeated to recover Resin A[hereinafter referred to as "Resin A (3)"].

Resin A (3) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 8,900.

Synthesis Example 7

Into the same separable flask as used in Synthesis Example 1 werecharged the following materials:

    ______________________________________                                        m-Cresol           74.2   g (0.687 mol)                                       p-Cresol           37.1   g (0.344 mol)                                       2,3,5-Trimethylphenol                                                                            14.0   g (0.103 mol)                                       Formalin           125.3  g (1.545 mol)                                       Oxalic acid dihydrate                                                                            1.558  g (0.0124 mol)                                      ______________________________________                                    

The separable flask was immersed in an oil bath, and polycondensationwas effected for 30 minutes with stirring while maintaining the flaskinterior at 100° C. Then, the following materials were added:

    ______________________________________                                        m-Cresol            18.6   g (0.172 mol)                                      2,3,5-Trimethylphenol                                                                             56.1   g (0.413 mol)                                      ______________________________________                                    

Polycondensation was effected for a further 2 hours to synthesize ResinA. After the completion of the reaction, the temperature of the oil bathwas increased to 180° C., and simultaneously the pressure inside thereaction vessel was reduced to 30-40 mmHg to remove water, oxalic acid,unreacted formaldehyde and unreacted phenols. The same subsequentprocedure as in Synthesis Example 1 was repeated to recover Resin A[hereinafter referred to as "Resin A (4)"].

Resin A (4) was dissolved in tetradhydrofuran to measure its Mw. The Mwwas 9,200.

Example 1

In 334 g of ethyl cellosolve acetate were dissolved 75 g of Resin A (1),25 g of Resin B (1) and 30 g of a condensate of 1 mole of2,3,4,4'-tetrahydroxybenzophenone and 2.5 moles of NQD-5 (the condensateis hereinafter referred to as "1,2-Quinonediazide I"). The resultingsolution was filtered through a membrane filter having a pore diameterof 0.2 μm to prepare a solution of Composition A. The solution wascoated on a silicon wafer having formed thereon a silicon oxide film, bymeans of a spinner. The coated wafer was subjected to prebaking on a hotplate at 90° C. for 2 minutes to form a resist film having a thicknessof 1.2 μm. The resist properties were measured. The results are shown inTable 1.

Example 2

A solution of Composition A was prepared by repeating the same procedureas in Example 1, except that the 1,2-Quinonediazide I was replaced by acondensate of 1 mole of 2,3,4-trihydroxybenzophenone and 2.5 moles ofNQD-5 (the condensate is hereinafter referred to as "1,2-QuinonediazideII"). A resist film was formed from the solution in the same manner asin Example 1, and measured for properties. The results are shown inTable 1.

Example 3

A solution of Composition A was prepared by repeating the same procedureas in Example 1, except that Resin A (1) and Resin B (1) were replacedby Resin A (2) and Resin B (3), respectively. A resist film was formedfrom the solution in the same manner as in Example 1, and measured forproperties. The results are shown in Table 1.

Example 4

A solution of Composition A was prepared by repeating the same procedureas in Example 1, except that Resin B (1) was replaced by Resin B (2). Aresist film was formed from the solution in the same manner as inExample 1, and measured for properties. The results are shown in Table1.

Example 5

A solution of Composition A was prepared by repeating the same procedureas in Example 1, except that 1,2-Quinonediazide I was replaced by1,2-Quinonediazide II. A resist film was formed from the solution in thesame manner as in Example 1, and measured for properties. The resultsare shown in Table 1.

Example 6

A solution of Composition A was prepared by repeating the same procedureas in Example 1, except that Resin A (1) was replaced by Resin A (2). Aresist film was formed from the solution in the same manner as inExample 1, and measured for properties. The results are shown in Table1.

Example 7

A solution of Composition A was prepared by repeating the same procedureas in Example 1, except that Resin A (1) and Resin B (1) were replacedby Resin A (2) and Resin B (3), respectively. A resist film was formedfrom the solution in the same manner as in Example 1, and measured forproperties. The results are shown in Table 1.

Example 8

A solution of Composition A was prepared by repeating the same procedureas in Example 1, except that Resin A (1) was replaced by Resin A (3). Aresist film was formed from the solution in the same manner as inExample 1, and measured for properties. The results are shown in Table1.

Example 9

A solution of Composition A was prepared by repeating the same procedureas in Example 1, except that Resin A (1) was replaced by Resin A (4). Aresist film was formed from the solution in the same manner as inExample 1, and measured for properties. The results are shown in Table1.

Comparative Example 1

A solution of a resin composition was prepared by repeating the sameprocedure as in Example 1, except that the amount of Resin A (1) wasincreased to 100 g and no Resin B was used. A resist film was formedfrom the solution in the same manner as in Example 1, and measured forproperties. The results are shown in Table 1.

Comparative Example 2

A solution of a resin composition was prepared by repeating the sameprocedure as in Example 1, except that the amounts of Resin A (1) andResin B (1) were changed to 40 g and 60 g, respectively. A resist filmwas formed from the solution in the same manner as in Example 1, andmeasured for properties. The results are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                                             Ethyl cello-                                Resin A     Resin B     1,2-Quinonediazide                                                                      solve acetate                                      Amount      Amount   Amount                                                                              Amount                                      Type                                                                              Mw (g)  Type                                                                              Mw (g)  Type                                                                              (g)   (g)                                  __________________________________________________________________________    Example                                                                            1 A (1)                                                                             8100                                                                             75   B (1)                                                                             590                                                                              25   I   30    334                                       2 "   "  "    "   "  "    II  "     "                                         3 A (2)                                                                             7500                                                                             "    B (3)                                                                             670                                                                              "    I   "     "                                         4 A (1)                                                                             8100                                                                             "    B (2)                                                                             610                                                                              "    I   "     "                                         5 "   "  "    "   "  "    II  "     "                                         6 A (2)                                                                             7500                                                                             "    B (1)                                                                             590                                                                              "    I   "     "                                         7 "   "  "    B (3)                                                                             670                                                                              "    I   "     "                                         8 A (3)                                                                             8900                                                                             "    B (1)                                                                             590                                                                              "    I   "     "                                         9 A (4)                                                                             9200                                                                             "    "   "  "    I   "     "                                    Comparative                                                                          A (1)                                                                             8100                                                                             100  --  -- --   I   "     "                                    Example                                                                            1                                                                             2 "   "  40   B (1)                                                                             590                                                                              60   I   "     "                                    __________________________________________________________________________                    Evaluation results                                                                        Yield of residual                                                                            Heat                                               Sensitivity                                                                         Resolution                                                                          film thickness                                                                         Developa-                                                                           resistance                                         (msec)                                                                              (μm)                                                                             (%)      bility                                                                              (°C.)                       __________________________________________________________________________             Example                                                                            1 200   0.50  99       Good  155                                              2 230   "     90       "     150                                              3 220   "     99       "     155                                              4 240   "     "        "     "                                                5 200   "     98       "     150                                              6 "     "     99       "     155                                              7 210   "     "        "     "                                                8 220   "     "        "     "                                                9 240   "     "        "     "                                           Comparative                                                                          500   0.55  "        Poor  160                                         Example                                                                            1                                                                             2 110   0.60  95       Good  130                                __________________________________________________________________________

Synthesis Example 8

Into the same separable flask as used in Synthesis Example 1 werecharged the following materials:

    ______________________________________                                        m-Cresol           120.0  g (1.11 mol)                                        p-Cresol           80.0   g (0.74 mol)                                        Formalin           37.5   g (0.462 mol)                                       Oxalic acid dihydrate                                                                            0.559  g (0.00443 mol)                                     ______________________________________                                    

The separable flask was immersed in an oil bath, and the flask contentswere subjected to polycondensation for 30 minutes with stirring whilemaintaining the flask interior at 100° C. to synthesize Resin B. Afterthe completion of the reaction, the temperature of the oil bath waselevated to 180° C., and simultaneously the pressure inside the reactionvessel was reduced to 30-40 mmHg to remove water, oxalic acid, unreactedformalin and unreacted phenols. The resulting molten resin was cooled toroom temperature to recover Resin B [hereinafter referred to as "Resin B(4)"].

Resin B (4) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 610.

Synthesis Example 9

Into the same separable flask as used in Synthesis Example 1 werecharged 10.0 g of Resin B (4) and 11.7 g of NQD-5. Then, 107 g ofacetone was added. The resulting mixture was stirred to obtain asolution. After the temperature of the flask interior was adjusted to30° C., 4.7 g of triethylamine was slowly dropped thereinto from adropping funnel while the temperature of the flask interior wascontrolled so as not to exeed 35° C. The resulting precipitate oftriethylamine hydrochloride was removed by filtration. The filtrate waspoured into a large amount of diluted hydrochloric acid to precipitate acondensate of Resin B (4) with NQD-5 [the condensate is hereinafterreferred to as "Resin C (1)"]. Resin C (1) was recovered by filtrationand dried at 40° C. for 24 hours. The dry weight was measured and theyield was 90%.

Resin C (1) was dissolved in tetrahydrofruan to measure its Mw. The Mwwas 750.

Synthesis Example 10

The same procedure as in synthesis Example 8 was repeated, except thatthe following materials were used, to recover Resin B [hereinafterreferred to as "Resin B (5)"]:

    ______________________________________                                        m-Cresol           152.2  g (1.407 mol)                                       2,3,5-Trimethylphenol                                                                            47.8   g (0.351 mol)                                       Formalin           35.7   g (0.44 mol)                                        Oxalic acid dihydrate                                                                            0.532  g (0.00422 mol)                                     ______________________________________                                    

The Resin B (5) was dissolved in tetrahydrofuran to measure its Mw. TheMw was 630.

Synthesis Example 11

The same procedure as in Synthesis Example 9 was repeated, except that10.0 g of Resin B (4) was replaced by 6.0 g of Resin B (5), to recoverResin C [hereinafter referred to as "Resin C (2)"].

Resin C (2) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 790.

Synthesis Example 12

Into the same separable flask as used in Synthesis Example 1 werecharged the following materials:

    ______________________________________                                        m-Cresol           27.0   g (0.25 mol)                                        3,5-Xylenol        52.2   g (0.427 mol)                                       Formalin           130.0  g (1.602 mol)                                       Oxalic acid dihydrate                                                                            1.458  g (0.0116 mol)                                      ______________________________________                                    

The separable flask was immersed in an oil bath, and the flask contentswere subjected to polycondensation for 30 minutes with stirring whilemaintaining the flask interior at 100° C. Then, the following materialswere added:

    ______________________________________                                        m-Cresol          107.8  g (0.997 mol)                                        3,5-Xylenol       13.0   g (0.106 mol)                                        ______________________________________                                    

Polycondensation was effected for a further 1 hour to synthesize ResinA. The same subsequent procedure as in Synthesis Example 8 was repeatedto recover Resin A [hereinafter referred to as "Resin A (5)"].

Resin A (5) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 9,200.

Synthesis Example 13

Into the same separable flask as used in Synthesis Example 1 werecharged the following materials:

    ______________________________________                                        m-Cresol           121.7  g (1.125 mol)                                       2,3,5-Trimethylphenol                                                                            9.6    g (0.070 mol)                                       Formalin           129.0  g (1.589 mol)                                       Oxalic acid dihydrate                                                                            1.596  g (0.0127 mol)                                      ______________________________________                                    

The separable flask was immersed in an oil bath, and the flask contentswere subjected to polycondensation for 1.5 hours with stirring whilemaintaining the flask interior at 100° C. Then, the following materialswere added:

    ______________________________________                                        m-Cresol           30.4   g (0.281 mol)                                       2,3,5-Trimethylphenol                                                                            38.3   g (0.281 mol)                                       ______________________________________                                    

Polycondensation was effected for a further 2.5 hours to synthesizeResin A. The same subsequent procedure as in Synthesis Example 8 wasrepeated to recover Resin A [hereinafter referred to as "Resin A (6)"].

Resin A (6) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 10,100.

Synthesis Example 14

The same procedure as in Synthesis Example 8 was repeated, except thatthe following materials were used, to recover Resin B [hereinafterreferred to as "Resin B (6)"]:

    ______________________________________                                        m-Cresol           80.0   g (0.74 mol)                                        p-Cresol           120.0  g (0.11 mol)                                        Formalin           37.5   g (0.462 mol)                                       Oxalic acid dihydrate                                                                            0.559  g (0.00443 mol)                                     ______________________________________                                    

Resin B (6) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 580.

Synthesis Example 15

The same procedure as in Synthesis Example 9 was repeated, except that10.0 g of Resin B (4) was replaced by 10.0 g of Resin B (6), to recoverResin C [hereinafter referred to as "Resin C (3)"].

Resin C (3) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 710.

Synthesis Example 16

Into the same separable flask as used in Synthesis Example 1 werecharged the following materials:

    ______________________________________                                        m-Cresol           82.6   g (0.764 mol)                                       p-Cresol           37.6   g (0.348 mol)                                       2,3,5-Trimethylphenol                                                                            11.8   g (0.087 mol)                                       Formalin           126.9  g (1.564 mol)                                       Oxalic acid dihydrate                                                                            1.578  g (0.0125 mol)                                      ______________________________________                                    

The separable flask was immersed in an oil bath, and the flask contentswere subjected to polycondensation for 1 hour with stirring whilemaintaining the flask interior at 100° C. Then, the following materialswere added:

    ______________________________________                                        m-Cresol           20.7   g (0.191 mol)                                       2,3,5-Trimethylphenol                                                                            47.3   g (0.347 mol)                                       ______________________________________                                    

Polycondensation was effected for a further 2 hours to synthesize ResinA. The same subsequent procedure as in Synthesis Example 8 was repeatedto recover Resin A [hereinafter referred to as "Resin A (7)"].

Resin A (7) was dissolved in tetrahydrofuran to measure its Mw. The Mwwas 9,900.

Example 10

In 310 g of ethyl cellosolve acetate were dissolved 70 g of Resin A (1),10 g of Resin B (4), 20 g of Resin C (1) and 20 g of 1,2-QuinonediazideI. The resulting solution was filtered through a membrane filter havinga pore diameter of 0.2 μm to prepare a solution of Composition B. Thesolution was coated on a silicon wafer having formed thereon a siliconoxide film, by means of a spinner. The coated wafer was prebaked on ahot plate at 90° C. for 2 minutes to form a resist film having athickness of 1.2 μm. The resist film was measured for resist properties.The results are shown in Table 2.

Example 11

A solution of Composition B was prepared by repeating the same procedureas in Example 10, except that Resin B (4) was replaced by 10 g of ResinB (5) and Resin C (1) was replaced by 20 g of Resin C (2). A resist filmwas formed from the solution in the same manner as in Example 10 andmeasured for properties. The results are shown in Table 2.

Example 12

A solution of Composition B was prepared by repeating the same procedureas in Example 10, except that 80 g of Resin A (1), 5 g of Resin B (4),15 g of Resin C (2), 25 g of 1,2-Quinonediazide II and 310 g of ethylcellosolve acetate were used. A resist film was formed from the solutionin the same manner as in Example 10 and measured for properties. Theresults are shown in Table 2.

Example 13

A solution of Composition B was prepared by repeating the same procedureas in Example 10, except that 75 g of Resin A (1), 10 g of Resin B (5),15 g of Resin C (1), 25 g of a condensate of 1 mole of2,3,4,4'-tetrahydroxybenzophenone with 2.5 mols of NQD-4 (the condensateis hereinafter referred to as "1,2-Quinonediazide III") and 310 g ofethyl cellosolve acetate were used. A resist film was formed from thesolution in the same manner as in Example 10 and measured forproperties. The results are shown in Table 2.

Example 14

A solution of Composition B was prepared by repeating the same procedureas in Example 10, except that 80 g of Resin A (5), 10 g of Resin B (4),10 g of Resin C (2), 20 of 1,2-Quinonediazide I and 310 g of ethylcellosolve acetate were used. A resist film was formed from the solutionin the same manner as in Example 10 and measured for properties. Theresults are shown in Table 2.

Example 15

A solution of Composition B was prepared by repeating the same procedureas in Example 10, except that 70 g of Resin A (5), 5 g of Resin B (5),25 g of Resin C (1), 15 g of 1,2-Quinonediazide II and 310 g of ethylcellosolve acetate were used. A resist film was formed from the solutionin the same manner as in Example 10 and measured for properties. Theresults are shown in Table 2.

Example 16

A solution of Composition B was prepared by repeating the same procedureas in Example 10, except that 65 g of Resin A (6), 15 g of Resin B (4),20 g of Resin C (1), 20 g of a condensate of 1 mole of3'-methoxy-2,3,4,4'-tetrahydroxybenzophenone with 2.5 moles of NQD-5(the condensate is hereinafter referred to as "1,2-Quinonediazide IV")and 310 g of ethyl cellosolve acetate were used. A resist film wasformed from the solution in the same manner as in Example 10 andmeasured for properties. The results are shown in Table 2.

Example 17

A solution of Composition B was prepared by repeating the same procedureas in Example 10, except that 65 g of Resin A (6), 15 g of Resin B (4),20 g of Resin C (1), 15 g of 1,2-Quinonediazide III and 310 g of ethylcellosolve acetate were used. A resist film was formed from the solutionin the same manner as in Example 10 and measured for properties. Theresults are shown in Table 2.

Example 18

A solution of Composition B was prepared by repeating the same procedureas in Example 10, except that 75 g of Resin A (6), 20 g of Resin B (6),5 g of Resin C (3), 15 g of 1,2-Quinonediazide III and 310 g of ethylcellosolve acetate were used. A resist film was formed from the solutionin the same manner as in Example 10 and measured for properties. Theresults are shown in Table 2.

Example 19

A solution of Composition B was prepared by repeating the same procedureas in Example 10, except that 70 g of Resin A (7), 15 g of Resin B (4),15 g of Resin C (3), 20 g of 1,2-Quinonediazide I and 310 g of ethylcellosolve acetate were used. A resist film was formed from the solutionin the same manner as in Example 10 and measured for properties. Theresults are shown in Table 2.

Comparative Example 3

A solution of a resin composition was prepared by repeating the sameprocedure as in Example 10, except that 45 g of Resin A (6), 40 g ofResin B (4), 15 g of Resin C (1), 20 g of 1,2-Quinonediazide I and 310 gof ethyl cellosolve acetate were used. A resist film was formed from thesolution in the same manner as in Example 10 and measured forproperties. The results are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________                                                1,2-                                     Resin A      Resin B     Resin C     Quinonediazide                                   Amount      Amount      Amount  Amount                                Type                                                                              Mw  (g)  Type                                                                              Mw (g)  Type                                                                              Mw (g)  Type                                                                             (g)                            __________________________________________________________________________    Example                                                                            10                                                                              A(1)                                                                              8100                                                                              70   B(4)                                                                              610                                                                              10   C(l)                                                                              750                                                                              20   I  20                                  11                                                                              "   "   "    B(5)                                                                              630                                                                              "    C(2)                                                                              790                                                                              "    "  "                                   12                                                                              "   "   80   B(4)                                                                              610                                                                              5    "   "  15   II 25                                  13                                                                              "   "   75   B(5)                                                                              630                                                                              10   C(1)                                                                              750                                                                              "    III                                                                              "                                   14                                                                              A(5)                                                                              9200                                                                              80   B(4)                                                                              610                                                                              "    C(2)                                                                              790                                                                              10   I  20                                  15                                                                              "   "   70   B(5)                                                                              630                                                                              5    C(1)                                                                              750                                                                              25   II 15                                  16                                                                              A(6)                                                                              10100                                                                             65   B(4)                                                                              610                                                                              15   "   "  20   IV 20                                  17                                                                              "   "   "    "   "  "    "   "  "    III                                                                              15                                  18                                                                              "   "   75   B(6)                                                                              "  20   C(3)                                                                              710                                                                              5    "  "                                   19                                                                              A(7)                                                                              9900                                                                              70   B(4)                                                                              580                                                                              15   "   "  15   I  20                             Comparative                                                                          A(6)                                                                              10100                                                                             45   "   610                                                                              40   C(1)                                                                              750                                                                              15   "  "                              Example 3                                                                     __________________________________________________________________________                 Ethyl cello-                                                                         Evaluation results                                                     solve acetate      Yield of residual                                                                      Heat                                              Amount Sensitivity                                                                         Resolution                                                                          film thickness                                                                         resistance                                                                         Developa-                                    (g)    (msec)                                                                              (μm)                                                                             (%)      (°C.)                                                                       bility                          __________________________________________________________________________    Example    10                                                                              310    190   0.50  >99      150  Good                                       11                                                                              "      180   "     "        "    "                                          12                                                                              "      210   "     "        "    "                                          13                                                                              "      220   "     "        "    "                                          14                                                                              "      250   "     "        155  "                                          15                                                                              "      260   "     "        150  "                                          16                                                                              "      240   "     "        "    "                                          17                                                                              "      220   "     "        "    "                                          18                                                                              "      200   "     "        155  "                                          19                                                                              "      230   "     "        "    "                               Comparative  "      160   0.55   95      140  "                               Example    3                                                                  __________________________________________________________________________

Synthesis Example 17

Into 2000-ml autoclave were charged 86.5 g (0.8 mol) of m-cresol, 27.2 g(0.2 tool) of 2,3,5-trimethylphenol, 75.0 g (0.925 tool) of formalin(37% by weight aqueous formaldehyde solution), 7.56 g (0.06 mol) ofoxalic acid dihydrate, 384.5 g of dioxane and 77.5 g of water.Thereafter, the autoclave was immersed in an oil bath and the internaltemperature thereof was kept at 140° C. to effect polycondensation for 6hours. Thereafter, the internal temperature of the autoclave wasreturned to the neighborhood of room temperature, and the reactionmixture was taken out and allowed to stand until the suspension wasseparated to two layers, after which the resin layer was taken out.Thereto was added 432 g of ethyl cellosolve acetate, and unreactedformaldehyde, dioxane and water were removed by distillation underreduced pressure, to obtain an ethyl cellosolve acetate solution. Thesolution thus obtained was washed with water to remove the oxalic acidused as a catalyst and the ethyl cellosolve acetate and water wereremoved by distillation under reduced pressure to recover Resin A[hereinafter referred to as "Resin A (8)"].

Resin A (8) was dissolved in tetrahydrofuran, and subjected tomeasurement of Mw to find that it was 9,000.

Example 20

The same procedure as in Example 10 was repeated, except that 80 g ofResin A (8), 20 g of Resin B (4), 7.5 g of Resin C (1), 20 g of acondensate of 1 mole of 2,3,4,4'-tetrahydrobenzophenone and 4.0 mols ofNQD-5 (the condensate is hereinafter referred to as 1,2-QuinonediazideV), 306 g of ethyl cellosolve acetate and 76.5 g of ethyl2-hydroxypropionate were used, to prepare a solution of Composition B ofthis invention, and subsequently the solution was subjected toevaluation of resist properties. The results of the evaluation were asfollows:

Sensitivity: 210 msec, Resolution: 0.50 μm Yield of residual filmthickness: >99%, Heat resistance: 155° C., Developability: good.

Synthesis Example 18

Into the same separatory flask as in Synthesis Example 1 were charged104.0 g (0.962 mol) of m-cresol, 14.0 g (0.103 mol) of2,3,5-trimethylphenol, 125.3 g (1.544 mols) of 37% by weight aqueousformaldehyde solution (formalin) and 1.558 g (0.012 mol) of oxalic aciddihydrate, and the separatory flask was immersed in an oil bath to keepthe internal temperature at 100° C., at which condensation was effectedfor 1 hour with stirring. Thereafter, 26.0 g (0.240 mol) of m-cresol and56.1 g (0.412 mol) of 2,3,5-trimethylphenol were added to the reactionmixture, and the resulting mixture was subjected to polycondensation fora further two hours to synthesize Resin A. After completion of thereaction, the temperature of the oil bath was elevated to 180° C. andsimultaneously, the pressure in the flask was reduced to 30-50 mmHg toremove water, oxalic acid, unreacted formaldehyde, unreacted m-cresoland unreacted 2,3,5-trimethylphenol. Subsequently, molten Resin A wascooled to room temperature to recover Resin A [hereinafter referred toas "Resin A (9)"]. Resin A (9) was dissolved in tetrahydrofuran tomeasure its Mw. The Mw was 4,500.

Synthesis Example 19

Into the same separatory flask as in Synthesis Example 1 were charged27.0 g (0.250 mol) of m-cresol, 52.2 g (0.427 mol) of 3,5-xylenol, 130.3g (1.605 mols) of formalin and 0.731 g (0.0058 mol) of oxalic aciddihydrate, and the separatory flask was immersed in an oil bath to keepthe internal temperature at 100° C., at which condensation was effectedfor 35 minutes with stirring. Thereafter, 108.0 g (0.999 mol) ofm-cresol and 13.1 g (0.107 mol) of 5-xylenol were added to the reactionmixture, and the mixture was subjected to condensation for a further 90minutes to synthesize Resin A. After completion of the reaction, thetemperature of the oil bath was elevated to 180° C. and simultaneouslythe pressure in the flask was reduced to 30-50 mmHg to remove water,oxalic acid, unreacted formaldehyde, unreacted m-cresol, unreactedp-cresol and unreacted 3,5-xylenol. Subsequently, molten Resin A wascooled to room temperature to recover Resin A [hereinafter referred toas "Resin A (10)"]. Resin A (10) was dissolved in tetrahydrofuran tomeasure its Mw. The Mw was 3,500.

Synthesis Example 20

Into the same separatory flask as in Synthesis Example 1 were charged82.4 g (0.763 mol) of m-cresol, 11.8 g (0.087 mol) of2,3,5-trimethylphenol, 37.6 g (0.348 mol) of p-cresol, 127.0 g (1.565mols) of formalin and 1.578 g (0.0125 mol) of oxalic acid dihydrate, andthe flask was immersed in an oil bath. The resulting mixture wassubjected to condensation with stirring for 60 minutes while theinternal temperature was kept at 100° C. Thereafter, 0.6 g (0.191 mol)of m-cresol and 47.3 g (0.348 mol) of 2,3,5-trimethylphenol were added,and the resulting mixture was subjected to condensation for a further100 minutes to synthesize Resin A. After completion of the reaction, thetemperature of the oil bath was elevated to 180° C., and simultaneously,the pressure in the flask was reduced to 30-50 mmHg to remove water,oxalic acid, unreacted formaldehyde, unreacted m-cresol, unreactedp-cresol and unreacted 2,2,5-trimethylphenol. Subsequently, the moltenResin A was cooled to room temperature to recover a resin [hereinafterreferred to as "Resin A (11)"]. Resin A (11) was dissolved intetrahydrofuran to measure its Mw. The Mw was 5,100.

Synthesis Example 21

Into the same separatory flask as in Synthesis Example 1 were charged17.8 g (0.165 mol) of m-cresol, 53.4 g (0.438 mol) of 3,5-xylenol, 44.4g (0.411 mol) of p-cresol, 137.3 g (1.692 mols) of formalin and 0.146 g(0.00116 mol) of oxalic acid dihydrate, and the flask was immersed in anoil bath. The resulting mixture was subjected to condensation withstirring for 30 minutes while the internal temperature was kept at 100°C., and thereafter, 71.0 g (0.657 mol) of m-cresol and 13.4 g (0.110mol) of 3,5-xylenol were added thereto, after which the resultingmixture was subjected to condensation for a further 45 minutes tosynthesize Resin A. After completion of the reaction, the temperature ofthe oil bath was elevated to 180° C. and simultaneously the pressure inthe flask was reduced to 30-50 mmHg to remove water, oxalic acid,unreacted formaldehyde, unreacted m-cresol, unreacted p-cresol andunreacted 3,5-xylenol. Subsequently, molten Resin A was cooled to roomtemperature to recover Resin A [hereinafter referred to as "Resin A(12)"].Resin A (12) was dissolved in tetrahydrofuran to measure its Mw.The Mw was 3,300.

Synthesis Example 22

Into the same separatory flask as in Synthesis Example 1 were charged120.0 g (1.110 mols) of m-cresol, 80.0 g (0.740 mol) of p-cresol, 37.5 g(0.462 mol) of formalin and 0.559 g (0.00443 mol) of oxalic aciddihydrate, and the flask was immersed in an oil bath. The resultingmixture was subjected to condensation with stirring for 30 minutes whilethe internal temperature was kept at 100° C. to synthesize Resin B.After completion of the reaction, the temperature of the oil bath waselevated to 180° C. and simultaneously the pressure in the flask wasreduced to 30-40 mmHg to remove water, oxalic acid, unreactedformaldehyde, unreacted m-cresol and unreacted p-cresol. Subsequently,molten Resin B was cooled to room temperature to recover Resin B[hereinafter referred to as "Resin B (7)"]. Resin B (7) was dissolved intetrahydrofuran to measure its Mw. The Mw was 610.

Subsequently, 10.0 g of Resin B (7) (the number of OH groups=0.083 mol,provided that the number of OH groups is a value calculated by dividingthe weight of Resin B (7), 10.0 g, by the molecular weight of onerecurring unit ##STR7## 120.15, and 13.3 g (0.052 mol) of NQD-5 werecharged into the same separatory flask as in Synthesis Example 1, and107 g of acetone was further charged thereinto. They were stirred toform a solution. Into a dropping funnel was separately charged 5.8 g oftriethylamine, and the separatory flask was immersed in a water bathkept at 30° C. When the internal temperature of the flask becameconstant at 30° C., the triethylamine was gradually dropped into theflask so that the internal temperature did not exceed 35° C., afterwhich the triethylamine hydrochloride precipitated was removed byfiltration. The filtrate was poured into a large amount of dilutehydrochloric acid to precipitate an ester of Resin B (7) with NQD-5[hereinafter referred to as "Resin C (4)"]. This was recovered byfiltration and dried at 40° C. for 24 hours. The yield obtained bymeasuring the dry weight was 90%. Resin C (4) was dissolved intetrahydrofuran to measure its Mw. The Mw was 770.

Synthesis Example 23

The same procedure as in Synthesis Example 18 was repeated, except thatinto the same separatory flask as in Synthesis Example 1 were charged152.2 g (1.407 mols) of m-cresol, 47.8 g (0.351 mol) of2,3,5-trimethylphenol, 35.7 g (0.440 mol) of formalin and 0.532 g(4.22×10⁻³ mol) of oxalic acid dihydrate, to obtain Resin B [hereinafterreferred to as "Resin B (8)"]. Resin B (8) was dissolved intetrahydrofuran to measure its Mw. The Mw was 630.

Subsequently, 10.0 g of Resin B (8) [the number of OH groups=0.080 mol)and 15.0 g (0.056 mol) of NQD-4 were charged into the same separatoryflask as in Synthesis Example 1, and the resulting mixture was subjectedto the same subsequent treatment as in the case of Resin C (4) to obtainan ester of Resin C (4) with NQD-4 [hereinafter referred to as "Resin C(5)"]. The yield was 92%. Resin C (5) was dissolved in tetrahydrofuranto measure its Mw. The Mw was 830.

Synthesis Example 24

Into the same separatory flask as in Synthesis Example 1 were charged122 g (1.0 mol) of 2,6-dimethylphenol, 42.0 g (0.52 mol) of formalin and0.50 g (3.97×10⁻³ mol), and the separatory flask was immersed in an oilbath. The resulting mixture was subjected to polycondensation for 4hours while the internal temperature of the flask was kept at 100° C.,to synthesize Resin B. After completion of the reaction, the temperatureof the oil bath was elevated to 180° C. and simultaneously the pressurein the flask was reduced to 30-40 mmHg to remove water, oxalic acid,unreacted formaldehyde and unreacted 2,6-dimethylphenol. Subsequently,molten Resin B was cooled to room temperature to recover Resin B[hereinafter referred to as Resin B (9)]. Resin B (9) was dissolved intetrahydrofuran to measure its Mw. The Mw was 570. It was clarified thatResin B (9) was bis(3,5-dimethyl-4-hydroxyphenyl)methane by measuring ¹H-NMR and mass spectrum thereof.

Example 21

In 310 g of ethyl cellosolve acetate were dissolved 90 g of Resin A (9),10 g of Resin C (4) and 20 g of a condensate of 1 mol of2,3,4,4'-tetrahydroxybenzophenone with 3.6 mols of NQD-5 [hereinafterreferred to as "1,2-Quinonediazide (V)"], and the resulting solution wasfiltered through a membrane filter having a pore diameter of 0.2 μm, toprepare a solution of the present composition. The solution thusobtained was coated on a silicon wafer having a silicon oxide film bymeans of a spinner, and then prebaked on a hot plate at 90° C. for 2minutes, to form a resist film having a thickness of 1.2 μm. This resistfilm was subjected to a test for properties with regard to sensitivity,resolution, yield of residual film thickness, developability, heatresistance and exposure margin. The results are shown in Table 3.

Example 22

The same procedure as in Example 21 was repeated, except that 90 g ofResin A (9), 10 g of Resin C (4) and 20 g of a condensate of 1 mole of2,3,4,4'-tetrahydroxybenzophenone with 3.5 mols of NQD-4 [hereinafterreferred to as "1,2-Quinonediazide (VI)"] were used, to obtain acomposition of this invention. A resist formed from the composition wassubjected to a test for properties. The results are shown in Table 3.

Example 23

The same procedure as in Example 21 was repeated, except that 85 g ofResin A (10), 15 g of Resin C (4) and 20 g of a condensate of 1 mol of2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone with 3.7 mols of NQD-5[hereinafter referred to as "1,2-Quinonediazide (VII)"] were used, toobtain a composition of this invention. A resist formed from thiscomposition was subjected to a test for properties. The results areshown in Table 3.

Example 24

The same procedure as in Example 21 was repeated, except that 93 g ofResin A (9), 7 g of Resin C (4) and 20 g of 1,2-Quinonediazide (VII)were used, to obtain a composition of this invention. A resist formedfrom this composition was subjected to a test for properties. Theresults are shown in Table 3.

Example 25

The same procedure as in Example 21 was repeated, except that 90 g ofResin A (9), 10 g of Resin C (5) and 20 g of 1,2-Quinonediazide (V) wereused to obtain a composition of this invention. A resist formed fromthis composition was subjected to a test for properties. The results areshown in Table 3.

Example 26

The same procedure as in Example 21 was repeated, except that 80 g ofResin A (10), 20 g of Resin C (5) and 25 g of 1,2-Quinonediazide (V)were dissolved in 290 g of ethyl cellosolve acetate, to obtain acomposition of this invention. A resist formed from this composition wassubjected to a test for properties. The results are shown in Table 3.

Example 27

The same procedure as in Example 21 was repeated, except that 85 g ofResin A (11), 15 g of Resin C (5) and 20 g of 1,2-Quinonediazide (V)were used, to obtain a composition of this invention. A resist formedfrom this composition was subjected to a test for properties. Theresults are shown in Table 3.

Example 28

The same procedure as in Example 21 was repeated, except that 90 g ofResin A (12), 10 g of Resin C (4) and 20 g of 1,2-Quinonediazide (VI)were used, to obtain a composition of this invention. The results areshown in Table 3.

Example 29

The same procedure as in Example 21 was repeated, except that 80 g ofResin A (8), 20 g of Resin B (9), 7.5 g of Resin C (1), 20 g of acondensate of 1 mol of 2,3,4,4'-tetrahydroxybenzophenone with 4 mols ofNQD-5 [hereinafter referred to as "1,2-Quinonediazide (VIII)"], 306 g ofethyl cellosolve acetate and 76.5 g of ethyl 2-hydroxypropionate wereused, to obtain a composition of this invention. A resist formed fromthis composition was subjected to a test for properties. The results ofthe evaluation were as follows:

    ______________________________________                                        Sensitivity             190 msec.                                             Resolution              0.50 μm                                            Yield of residual film thickness                                                                      >99%                                                  Heat resistance         155° C.                                        Developability          Good                                                  ______________________________________                                    

Comparative Example 4

The same procedure as in Example 21 was repeated, except that 100 g ofResin A (9) and 20 g of 1,2-Quinonediazide (V) were used, to obtain acomposition. A resist formed from this composition was subjected to atest for properties. The results are shown in Table 3.

                                      TABLE 3                                     __________________________________________________________________________                                       1,2-Quinone-                               Resin A                Resin B     diazide                                                GPC   Amount      Amount  Amount                                       Type                                                                              Mw a/b                                                                              c/b                                                                              (g)  Type                                                                              Mw (g)  Type                                                                             (g)                                     __________________________________________________________________________    Ex.                                                                              21                                                                              A(9)                                                                              5400                                                                             0.90                                                                             0.51                                                                             90   C(4)                                                                              770                                                                              10   V  20                                      Ex.                                                                              22                                                                              "   "  "  "  "    "   "  "    VI "                                       Ex.                                                                              23                                                                              A(10)                                                                             3500                                                                             "  "  85   "   "  15   VII                                                                              "                                       Ex.                                                                              24                                                                              A(9)                                                                              4500                                                                             "  "  93   "   "  7    "  "                                       Ex.                                                                              25                                                                              "   "  "  "  90   C(5)                                                                              830                                                                              10   V  "                                       Ex.                                                                              26                                                                              A(10)                                                                             3500                                                                             0.70                                                                             0.72                                                                             80   "   "  20   "  25                                      Ex.                                                                              27                                                                              A(11)                                                                             5100                                                                             1.01                                                                             0.48                                                                             85   "   "  15   "  20                                      Ex.                                                                              28                                                                              A(12)                                                                             3300                                                                             0.67                                                                             0.65                                                                             90   C(4)                                                                              770                                                                              10   VI "                                       Comp.                                                                              A(9)                                                                              4500                                                                             0.90                                                                             0.51                                                                             100  --  -- --   V  "                                       Ex.                                                                              4                                                                          __________________________________________________________________________                  Results of evaluation                                                                  Yield of   Heat                                             Ethyl cellosolve                                                                       Sensi-                                                                            Resulu-                                                                            residual   resis-                                           acetate amount                                                                         tivity                                                                            tion thickness                                                                           Develop-                                                                           tance                                                                             Exposure                                     (g)      (msec)                                                                            (μm)                                                                            (%)   ability                                                                            (°C.)                                                                      margin                                  __________________________________________________________________________    Ex.                                                                              21                                                                              310      220 0.50 >99   Good 155 0.49                                    Ex.                                                                              22                                                                              "        240 "    "     "    "   0.50                                    Ex.                                                                              23                                                                              "        190 "    "     "    150 0.47                                    Ex.                                                                              24                                                                              "        290 "    "     "    155 0.58                                    Ex.                                                                              25                                                                              "        250 "    "     "    "   0.51                                    Ex.                                                                              26                                                                              290      "   "    "     "    150 0.44                                    Ex.                                                                              27                                                                              310      300 "    "     "    155 0.46                                    Ex.                                                                              28                                                                              "        230 "    "     "    "   0.52                                    Comp.                                                                              "        170 0.55 "     "    "   0.71                                    Ex.                                                                              4                                                                          __________________________________________________________________________

What is claimed is:
 1. A radiation sensitive resin compositionconsisting of (1) an alkali-soluble novolak resin, (2) a1,2-quinonediazide compound and (3) a solvent, wherein thealkali-soluble novolak resin consists of a mixture of:50-95 parts byweight of Resin A having a standard, polystyrene-reduced weight-averagemolecular weight of 2,000-20,000, wherein Resin A is (i) a resinobtained by polycondensation of phenolic ingredients consisting ofm-cresol phenol represented by structural formula (I) or (I'): ##STR8##wherein m is 2 or 3, with at least one aldehyde, (ii) a resin obtainedby polycondensation of phenolic ingredients consisting of m-cresol,p-cresol and at least one phenol represented by structural formula (I)or (I') with at least one aldehyde, or (iii) a combination of resins (i)and (ii), and - 45parts by weight of Resin B having a standard,polystyrene-reduced weight-average molecular weight of 200-2,000,wherein Resin B is a resin obtained by polycondensation of at least onephenol represented by the structural formula (II): ##STR9## wherein n is0, 1, 2 or 3, with at least one aldehyde, and - 50parts by weight ofResin C, wherein Resin C is an ester of Resin B with1,2-quinonediazidesulfonic acid.
 2. A radiation sensitive resincomposition consisting of (1) an alkali-soluble novolak resin, (2) a1,2-quinonediazide compound and (3) a solvent, wherein thealkali-soluble novolak resin consists of a mixture of:50-95 parts byweight of Resin A having a standard, polystyrene-reduced weight-averagemolecular weight of 2,000-20,000, wherein Resin A is (i) a resinobtained by polycondensation of phenolic ingredients consisting ofm-cresol and at least one of 2,3,5-trimethylphenol, 2,3-xylenol and3,4-xylenol, with at least one aldehyde, (ii) a resin obtained bypolycondensation of phenolic ingredients consisting of m-cresol,p-cresol and at least one of 2,3,5-trimethylphenol, 2,3-xylenol and3,4-xylenol with at least one aldehyde, or (iii) a combination of resins(i) and (ii), and 0-45 parts by weight of Resin B having a standardpolystyrene-reduced weight-average molecular weight of 200-2,000,wherein Resin B is a resin obtained by polycondensation of at least onephenol represented by the structural formula (II): ##STR10## wherein nis 0, 1, 2 or 3, with at least one aldehyde, and - 50parts by weight ofResin C, wherein Resin C is an ester of Resin B with1,2-quinonediazidesulfonic acid.
 3. A radiation-sensitive resincomposition consisting of (1) an alkali-soluble novolak resin, (2) a1,2-quinonediazide compound, (3) a solvent and (4) at least one of asensitizer, a surface active agent, a dye, a storage stability improver,a pigment and an antifoaming agent, wherein the alkali-soluble novolakresin consists of a mixture of:0-95 parts by weight of Resin A having astandard, polystyrene-reduced weight-average molecular weight of2,000-20,000, wherein Resin A is (i) a resin obtained bypolycondensation of phenolic ingredients consisting of m-cresol and atleast one phenol represented by structural formula (I) or (I'):##STR11## wherein m is 2 or 3, with at least one aldehyde, (ii) a resinobtained by polycondensation of phenolic ingredients consisting ofm-cresol, p-cresol and at least one phenol represented by formula (I) or(I') with at least one aldehyde, or (iii) a combination of resins (i)and (ii), and - 45parts by weight of Resin B having a standard,polystyrene-reduced weight-average molecular weight of 200-2,000,wherein Resin B is a resin obtained by polycondensation of at least onephenol represented by the structural formula (II): R1 ? ? ##STR12##wherein n is 0, 1, 2 or 3, with at least one aldehyde, and - 50parts byweight of Resin C, wherein Resin C is an ester of Resin B with1,2-quinonediazidesulfonic acid.
 4. A radiation-sensitive resincomposition consisting of (1) an alkali-soluble novolak resin, (2) a1,2-quinonediazide compound, (3) a solvent and (4) at least one of asensitizer, a surface active agent, a dye, a storage stability improver,a pigment and an antifoaming agent, wherein the alkali-soluble novolakresin consists of a mixture of:50-95 parts by weight of Resin A having astandard, polystyrene-reduced weight-average molecular weight of2,000-20,000, wherein Resin A is (i) a resin obtained bypolycondensation of phenolic ingredients consisting of m-cresol and atleast one of 2,3,5-trimethylphenol, 2,3-xylenol and 3,4-xylenol, with atleast one aldehyde, (ii) a resin obtained by polycondensation ofphenolic ingredients consisting of m-cresol, p-cresol and at least oneof 2,3,5-trimethylphenol, 2,3-xylenol and 3,4-xylenol with at least onealdehyde, or (iii) a combination of resins (i) and (ii), and 0-45 partsby weight of Resin B having a standard polystyrene-reducedweight-average molecular weight of 200-2,000, wherein Resin B is a resinobtained by polycondensation of at least one phenol represented by thestructural formula (II): ##STR13## wherein n is 0, 1, 2 or 3, with atleast one aldehyde, and - 50parts by weight of Resin C, wherein Resin Cis an ester of Resin B with 1,2-quinonediazidesulfonic acid.
 5. Aradiation-sensitive resin composition according to claim 1 or 3, whereinthe phenol represented by the structural formula (I) or (I') is selectedfrom the group consisting of 2,3-xylenol, 2,5-xylenol, 3,4-xylenol,3,5-xylenol, 2,3,5-trimethylphenol and 3,4,5-trimethylphenol.
 6. Aradiation-sensitive resin composition according to claim 1 or 3, whereinthe phenol represented by the structural formula (II) is selected fromthe group consisting of phenol, o-cresol, m-cresol, 2,3-xylenol,2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol,3,6-xylenol, 2,3,5-trimethylphenol and 3,4,5-trimethylphenol.
 7. Aradiation-sensitive resin composition according to claim 1 or 3, whereinthe aldehyde is selected from the group consisting of formaldehyde,paraformaldehyde, benzaldehyde, furfural and acetaldehyde.
 8. Aradiation-sensitive resin composition according to claim 1 or 3, whereinResin A has a standard polystyrene-reduced weight-average molecularweight of 4,000-20,000.
 9. A radiation-sensitive resin compositionaccording to claim 1 or 3, wherein Resin B has a standardpolystyrene-reduced weight-average molecular weight of 300-1,000.
 10. Aradiation-sensitive resin composition according to claim 1 or 3, whereinthe molar ratio of m-cresol/the phenol represented by the structuralformula (I) or (I') is 20/80 to 95/5.
 11. A radiation-sensitive resincomposition according to claim 1 or 3, wherein the molar ratio orm-cresol/p-cresol/the phenol represented by the structural formula (I)or (I') is 20-90/5-75/5-75 (the total of the three is 100 moles).
 12. Aradiation-sensitive resin composition according to claim 1 or 3, whereinin Resin A, the amount of the aldehyde used is 0.7-3 mole per mole ofthe phenol.
 13. A radiation-sensitive resin composition according toclaim 1 or 3, wherein in Resin B, the amount of the aldehyde used is0.1-1.5 moles per mole of the phenol.
 14. A radiation-sensitive resincomposition according to claim 1 or 3, wherein the1,2-quinonediazidesulfonic acid is 1,2-benzoquinonediazide-4-sulfonicacid, 1,2-naphthoquinonediazide-4-sulfonic acid,1,2-naphthoquinonediazide-4-sulfonic acid or1,2-naphthoquinonediazide-5-sulfonic acid.
 15. A radiation-sensitiveresin composition 1,2-quinonediazide according to claim 1 or 3, whereinthe compound is at least one compound selected from the group consistingof 1,2-benzoquinonediazide-4-sulfonic acid esters,1,2-naphthoquinonediazide-4-sulfonic acid esters and1,2-naphthoquinonediazide-5-sulfonic acid esters.
 16. Theradiation-sensitive resin composition according to claim 1 or 3, whereinthe standard polystyrene-reduced weight average molecular weight ofresin B ranges from 300 to 1,000.
 17. The radiation-sensitive resincomposition according to claim 1 or 3, which is employed formanufacturing a highly integrated circuit.